A method for preparing mycelium fiber leather by aldehyde-resin combination tanning

Abstract

The present invention belongs to the technical field of the production of novel leather-like mycelial fiber leather, and particularly relates to a method for preparing mycelial fiber leather by aldehyde-resin combination tanning. The method comprises the following steps: (1) Firstly, the mycelium is pretreated with an alkaline solution and an acidic solution to make the mycelium suitable for tanning; (2) An aldehyde group-containing tanning agent and an acrylic resin-based dispersing tanning agent are added for tanning; (3) Retanning is carried out in the acrylic resin-based dispersing tanning agent, then fats and oils and surfactants are added for reaction, and after washing and natural drying, a soft mycelial fiber leather is obtained. The process in the present invention can produce mycelial fiber leather with physical and chemical properties meeting the requirements of daily applications, which has a unique appearance and feel; the materials used in the processing process are all non-toxic and clean materials, ensuring the cleaning requirements for production and use.

Description

Technical Field

[0001] The present invention belongs to the technical field of the production of novel leather-like mycelial fiber leather, and particularly relates to a method for preparing mycelial fiber leather by aldehyde-resin combination tanning. Background Art

[0002] The leather industry has a long history. However, with the increasing emphasis on environmental sustainability in society, the environmental friendliness of leather production needs to be taken seriously. In recent years, the development of novel leather-like materials using plant-based materials such as mango peel, cactus peel, mycelium, etc. has received market attention. Among different plant-based materials, the mycelium of edible fungi such as mushrooms, shiitake mushrooms, and Hericium erinaceus for the production of leather-like materials has attracted great interest in the market. Mycelium is an aggregate of hyphae, which are crisscrossed and have diverse morphologies. Hyphae spread and extend in the substrate or culture medium, showing a repeatedly branched reticular structure. The reticular structure of mycelium is similar to the collagen fiber reticular structure in animal leather, making it possible to become a leather-like material. The components of mycelium mainly include chitin and other polysaccharides such as glucan, protein, chitosan, polyglucuronic acid, etc. Its sugar-based chemical properties make it have great differences from traditional leather production mainly based on collagen during cross-linking and binding. Aldehydes and resinous substances have the potential to bind to amino and hydroxyl groups in hyphae, which is theoretically feasible. Summary of the Invention

[0003] The purpose of the present invention is to provide a production method of novel mycelial fiber leather. Through aldehyde-resin combination tanning, the obtained mycelial fiber leather has a soft touch similar to traditional animal leather, and has good heat resistance and strength and toughness that meet the use requirements.

[0004] To achieve the above purpose, the present invention provides the following technical solutions

[0005] The present invention provides a method for preparing mycelial fiber leather by aldehyde-resin combination tanning, including the following steps:

[0006] (1) Pretreatment

[0007] Boil and inactivate the mycelium, then wash, weigh, and trim it. In an aqueous environment, first disperse the fibers of the mycelium, and then add an acidic solution to further treat the mycelium to make it suitable for tanning, obtaining the pretreated mycelium;

[0008] (2) Tanning

[0009] Debase and wash the pretreated mycelium obtained in step (1), and then add an aldehyde group-containing tanning agent and an acrylic resin-based dispersing tanning agent for tanning; after the reaction ends, wash the mycelial leather with water to obtain the mycelial leather to be retanned;

[0010] (3) Retanning

[0011] Immerse the mycelium skin to be retanned in step (2) in the acrylic resin-based dispersing tanning agent described in step (2) for retanning, then add oil and surfactant for reaction, and obtain a soft mycelium fiber skin after washing and natural drying.

[0012] Preferably, in step (1), the liquor ratio for pretreatment is 100%-150%, and the temperature is 25-30°C.

[0013] Preferably, the substance for dispersing the mycelium fibers in step (1) is an alkaline substance, selected from calcium hydroxide, sodium hydroxide, potassium hydroxide or aluminum hydroxide with a dosage of 0.01%-10% based on the weight of the skin.

[0014] More preferably, in step (1), the pH is adjusted >10 with an alkaline substance, and the treatment time with the alkaline substance is 8-24 h.

[0015] Preferably, the acidic solution in step (1) is selected from oxalic acid, hydrochloric acid, sulfuric acid, ethanedioic acid, acetic acid, phosphoric acid or boric acid with a dosage of 0.01%-5% based on the weight of the skin.

[0016] Preferably, the pH value after adjusting with the acidic solution in step (1) is 4-8, and the treatment time with the acidic solution is 3-5 h.

[0017] In step (1), according to the natural characteristics of the mycelium, the mycelium structure is adjusted by using acid / alkali to disperse its fibers. First, an alkaline substance is added to adjust the pH>10 to change the mycelium structure, so that the mycelium reaches a soft and fiber-dispersed state. Subsequently, an acidic solution is added to adjust the pH to 4-8, making the aldehyde group-containing tanning agent and the acrylic resin-based dispersing tanning agent suitable for penetration and combination.

[0018] The tanning in step (2) can improve the strength and stability of the mycelium.

[0019] Preferably, the aldehyde group-containing tanning agent in step (2) is selected from modified glutaraldehyde, nonanal, citral, cinnamaldehyde or lily aldehyde, and the dosage is 1%-10% of the mass of the mycelium.

[0020] Preferably, the acrylic resin-based dispersing tanning agent in step (2) is selected from methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic resin or methacrylic resin, and the dosage is 1%-10% of the mass of the mycelium.

[0021] Preferably, the tanning process in step (2) is carried out in an aqueous environment or an organic solvent environment miscible with water.

[0022] Preferably, for the tanning in step (2), the liquor ratio is 80%-150%, the reaction temperature is 25-60°C, and the total reaction time is 8-24 h.

[0023] Further preferably, after adding the aldehyde group-containing tanning agent in step (2), the reaction is carried out for 4-24 h, and then an acrylic resin-based dispersing tanning agent is added for tanning.

[0024] Preferably, the reaction temperature for retanning in step (3) is 30-60 °C, the reaction is carried out for 5-24 h, and after adding the grease, the reaction temperature is 40-60 °C, and the reaction is carried out for 3-6 h.

[0025] Preferably, in step (3), the grease used is animal grease, and the dosage of the grease is 3%-30% of the weight of the mycelium skin after tanning; the liquor ratio is 50%-150%.

[0026] Preferably, in step (3), the surfactant is Tween or sodium dodecyl sulfonate, and the dosage is 0.3%-5% of the mass of the mycelium.

[0027] The present invention also provides a mycelial fiber skin prepared by the above method.

[0028] Advantages of the present invention

[0029] (1) The process in the present invention can produce a mycelial fiber skin with physical and chemical properties meeting the daily application requirements, which has a unique appearance and feel.

[0030] (2) The materials used in the processing process of the present invention are all non-toxic and clean materials, ensuring the cleaning requirements of production and use. Description of the drawings

[0031] Figure 1 It is a diagram of the grain surface state of the mycelial fiber skin before tanning after pretreatment in Example 2;

[0032] Figure 2 It is a diagram of the grain surface state of the mycelial fiber skin after retanning in Example 2;

[0033] Figure 3 It is a microscopic state diagram of the mycelial fiber skin after retanning in Example 2. Detailed implementation manners

[0034] The present invention will be described below through specific implementation schemes. Unless otherwise specified, the technical means used in the present invention are all methods well-known to those skilled in the art. In addition, the implementation schemes should be understood as illustrative and not limiting the scope of the present invention. The essence and scope of the present invention are only defined by the claims. For those skilled in the art, various changes or modifications to the material components and dosages in these implementation schemes without departing from the essence and scope of the present invention also belong to the protection scope of the present invention.

[0035] Example 1

[0036] A method for preparing a mycelial fiber skin by aldehyde-resin combination tanning, comprising the following steps:

[0037] (1) Pretreatment: Boil the mycelium to inactivate it, wash it, weigh it, and trim it; add 0.01% sodium hydroxide to the rotary drum, liquor ratio 150%, pH 13, react at 25°C for 24 h, wash, and then add 0.1% oxalic acid based on the weight of the mycelium every 30 min until the pH value reaches 8, and then rotate for 3 h.

[0038] (2) Tanning: Debark and wash the mycelium pretreated in step (1), add 5% citral, react at 25°C for 10 h, add 10% acrylic resin tanning agent, liquor ratio 100%, react at 30°C for 12 h, drain the liquid, wash, and obtain the mycelium skin to be retanned.

[0039] (3) Retanning: Immerse the mycelium in a 10% hydroxyethyl acrylate solution, react at 30°C for 8 h, and wash. Add 10% fish oil and 2% Tween, liquor ratio 50%, react at 45°C for 4 h, wash, and dry naturally to obtain a soft mycelium fiber skin.

[0040] Example 2

[0041] A method for preparing mycelium fiber skin by aldehyde-resin combination tanning, comprising the following steps:

[0042] (1) Pretreatment: Boil the cleaned mycelium to inactivate it and weigh it as the reference weight for subsequent material addition; add 2% calcium hydroxide, 0.5% sodium chloride, liquor ratio 120%, pH 12.5, oscillate at 25°C for 12 h, wash, add 5% oxalic acid and 100% water, pH 6, oscillate for 4 h.

[0043] The grain surface state diagram of the mycelium after the obtained pretreatment is as shown in Figure 1 as shown. It has a lamellar state similar to that of traditional animal raw hides and can be used for leather production.

[0044] (2) Tanning: Debark and wash the mycelium pretreated in step (1), water consumption 100%, add 10% modified glutaraldehyde, react at 25°C for 10 h, add 10% acrylic resin, react at 40°C for 10 h. Wash, take out and let stand for 12 h to obtain the mycelium skin to be retanned.

[0045] (3) Retanning: Immerse the mycelium in a 10% methyl methacrylate resin solution, liquor ratio 80%, react at 30°C for 8 h. Add 5% emulsified bovine hoof oil and 1% Tween, react at 50°C for 5 h, wash, and dry naturally to obtain a soft mycelium fiber skin.

[0046] The surface morphology of the obtained mycelium fiber skin is as shown in Figure 2 as shown, and the micro scanning electron microscope image is as shown in Figure 3As shown in []. The results show that after tanning, its surface is transformed from the original mycelium state with slight cracks to a relatively flat and uniform leather state. The performance indexes of the obtained mycelium fiber leather are shown in Table 1.

[0047] Table 1. Physical and chemical properties of mycelium fiber leather in Example 2

[0048] Tear strength (KN / m) Elongation at break % Shrinking temperature / °C Example 2 5.2 49.9 150℃

[0049] Example 3

[0050] A method for preparing mycelium fiber leather by aldehyde-resin combination tanning, comprising the following steps:

[0051] (1) Pretreatment: Boil and inactivate the cleaned mycelium, weigh it, and use it as the reference weight for subsequent material addition; liquor ratio 100%, add 0.05% sodium hydroxide, pH 13, react for 8 h, take out and wash, then add 0.5% acetic acid every 30 min to adjust the pH to 5, and react at 30 °C for 3 h.

[0052] (2) Tanning: Debase and wash the mycelium pretreated in step (1), liquor ratio 100%, add 5% cinnamaldehyde and react at 25 °C for 6 h, then wash. Add 10% methyl methacrylate resin, oscillate at 30 °C for 12 h, wash, and obtain the mycelium leather to be retanned. (3) Retanning: Immerse the mycelium in a 10% methyl acrylate solution, liquor ratio 100%, react at 30 °C for 6 h. Add 5% fish oil and 1% Tween 20, react at 45 °C for 4 h, wash, and dry naturally to obtain the soft mycelium fiber leather.

Claims

1. A method for preparing mycelial fiber leather by aldehyde-resin combination tanning, characterized in that, The steps are as follows: (1)Pretreatment Boil the mycelium to inactivate it, then wash, weigh, and trim it. In an aqueous environment, first disperse the fibers of the mycelium, and then add an acidic solution to further treat the mycelium to make it suitable for tanning, obtaining the pretreated mycelium; (2)Tanning Flesh the pretreated mycelium obtained in step (1) and wash it, then add an aldehyde group-containing tanning agent and an acrylic resin-based dispersion tanning agent for tanning; after the reaction ends, wash the mycelium skin with water to obtain the mycelium skin to be retanned; (3)Retanning Immerse the mycelium skin to be retanned in step (2) in the acrylic resin-based dispersion tanning agent described in step (2) for retanning, then add oil and a surfactant for reaction, and after washing and natural drying, obtain a soft mycelium fiber skin; In step (1), the liquor ratio for pretreatment is 100%-150%; the substance for dispersing the mycelium fibers in step (1) is an alkaline substance, and the treatment time with the alkaline substance is 8-24 h; the treatment time with the acidic solution is 3-5 h; In step (2), after adding the aldehyde group-containing tanning agent, react for 4-24 h, and then add the acrylic resin-based dispersion tanning agent for tanning.

2. The method for preparing hyphal fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, In step (1), the temperature for pretreatment is 25-30 °C.

3. A method for preparing mycelium fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, The alkaline substance is selected from calcium hydroxide, sodium hydroxide, potassium hydroxide, or aluminum hydroxide with a dosage of 0.01%-10% of the skin weight.

4. A method for preparing mycelium fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, In step (1), use the alkaline substance to adjust the pH>10.

5. A method for preparing mycelium fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, The acidic solution in step (1) is selected from oxalic acid, hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, phosphoric acid, or boric acid with a dosage of 0.01%-5% of the skin weight.

6. A method for preparing hyphae fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, The pH value adjusted by adding the acidic solution in step (1) is 4-8.

7. A method for preparing mycelium fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, The aldehyde group-containing tanning agent in step (2) is selected from modified glutaraldehyde, nonanal, citral, cinnamaldehyde, or lily aldehyde, and the dosage is 1%-10% of the mass of the mycelium.

8. A method for preparing mycelium fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, The acrylic resin-based dispersion tanning agent in step (2) is selected from methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or acrylic resin, and the dosage is 1%-10% of the mass of the mycelium.

9. The method for preparing hyphal fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, In step (2), the tanning process is carried out in an aqueous environment or an organic solvent environment miscible with water.

10. A method for preparing hyphal fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, In step (2), for the tanning, the liquor ratio is 80%-150%, the reaction temperature is 25-60 °C, and the total reaction time is 8-24 h.

11. A method for preparing hyphal fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, In step (3), the reaction temperature for retanning is 30-60 °C, the reaction time is 5-24 h, and after adding the oil, the reaction temperature is 40-60 °C, and the reaction time is 3-6 h.

12. A method for preparing hyphal fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, In step (3), the oil used is animal oil, and the dosage of the oil is 3%-30% of the skin weight of the tanned mycelium; the liquor ratio is 50%-150%.

13. A method for preparing hyphae fiber leather by aldehyde-resin combination tanning according to claim 1, characterized in that, In step (3), the surfactant is Tween or sodium dodecyl sulfate, and the dosage is 0.3%-5% of the mass of the mycelium.

14. The mycelium fiber skin prepared by the method according to any one of claims 1-13.

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